The present invention relates to new synthetic resin compositions prepared by reacting cyclopentadienes with tall oil pitch or a neutrals-containing component thereof, and to methods of using the same in coatings, inks and the like.
Tall oil is a by-product of the pulping process. This by-product can be further refined, that is, separated into its component parts, by a process of fractional distillation, such as is described in Tall Oil, J. Drew and M. Post, eds., pp. 87-97, Pulp Chemical Association (1981). A wide variety of process systems and conditions have been employed by the art in carrying out this distillation. Sisson et al., U.S. Pat. No. 2,894,880, for example, describes in detail the fractional distillation of tall oil using a combination of distillation towers and falling film reboilers.
The literature is replete with publications describing the reaction of refined tall oil, and the tall oil fatty acid and tall oil rosin chemical constituents thereof, with dicyclopentadiene or similar monomers to produce synthetic resin precursors. Peters, U.S. Pat. Nos. 2,598,424 and 2,598,425, for example, discuss a process for the preparation of resinous material comprising reacting dicyclopentadiene with refined tall oil and tall oil rosin. Malatesta, U.S. Pat. No. 4,292,221, describes the copolymerization of tall oil fatty acid with dicyclopentadiene in the production of resins useful in inks. Laurito, U.S. Pat. Nos. 4,443,100, 4,189,410 and 4,056,498, disclose the reaction of distilled tall oil with dicyclopentadiene to produce ink resins.
Another important co-product of the distillation of tall oil is tall oil pitch. Sisson et al., U.S. Pat. No. 2,894,880, obtains a high grade of tall oil pitch melting at 40.degree. C. which represents 17% of tall oil feed. Tall oil pitch is described in detail in Kirk-Othmer Encyclopedia of Chemical Technology, H. Mark, J. McKetter and D. Othmer, eds., Vol. 19, pp. 614-619 (2nd ed. 1969). A thorough analysis of tall oil pitch is also provided in Era et al., J. Amer. Oil Chem. Soc., Vol. 56, pp. 992-994 (1979), and Holmbom et al., J. Amer. Oil Chem. Soc., Vol. 55, pp. 342-344 (1978). In Holmbom et al., J. Amer. Oil Chem. Soc., Vol. 55, pp. 342-344 (1978), at page 342, an analysis of untreated tall oil pitch from different Finnish and American sources is reported. This analysis reads as follows:
______________________________________ Properties of Tall Oil Pitch Grades GRADE A B C D E F ______________________________________ Yield, of crude 25 25 25 30 20 20 tall oil (%) Acid number 34 49 38 39 30 27 (mg KOH/g) Saponification 94 115 111 105 106 101 number (mg KOH/g) Softening 46 30 25-30 36 -- -- point (.degree.C.) Resin Acids (%) 13 17 16 11 9 11 Insolubles in 2 7 10 10 9 0.4 petroleum ether (%) ______________________________________
This publication also notes that these six grades contain 34.6 to 51.6% free acids, the balance being neutral pitch consisting of esterified acids and unsaponifiable neutral compounds. In Era et al., J. Amer. Oil Chem. Soc., Vol. 56, pp. 992-994 (1979), the authors state that the ash content of six different tall oil pitch samples from Finnish and American sources range from about 0.1 to 1.4%.
Tall oil pitch has long been recognized in the industry as a most useful reagent in the preparation of valuable products and derivatives. Speck et al., U.S. Pat. No. 3,238,164, for example, illustrates the use of tall oil pitch in the preparation of pitch esters. D'Agostino, U.S. Pat. No. 3,445,409, describes the use of tall oil pitch in epoxy coatings. Szita, U.S. Pat. No. 4,337,193, discusses additives which increase the hardness of tall oil pitch, making the pitch useful in coating compositions.
New and/or better uses for tall oil pitch are being sought. The present invention is directed to this end.